Anderson-type heteropoly compound-based catalyst compositions and their use conversion of synthesis gas to oxygenates

ABSTRACT

Use a transition metal-containing, Anderson-type heteropoly compound catalyst to convert synthesis gas to an oxygenate, especially an alcohol that contains from one carbon atom to six carbon atoms.

This application is a non-provisional application claiming priority fromthe U.S. Provisional Patent Application No. 61/391,735, filed on Oct.11, 2010, entitled “ANDERSON-TYPE HETEROPOLY COMPOUND-BASED CATALYSTCOMPOSITIONS AND THEIR USE CONVERSION OF SYNTHESIS GAS TO OXYGENATES”the teachings of which are incorporated by reference herein, as ifreproduced in full hereinbelow.

This invention relates generally to catalyst compositions based upon aAnderson-type structure heteropoly compound and their use in convertingsynthesis gas (syngas, a mixture of carbon monoxide (CO) and hydrogen(H₂)) to oxygenates, especially alcohols that contain from two to sixcarbon atoms (C₂ to C₆).

Syngas conversion processes employ a variety of catalysts that, in turn,tend to yield a mixture of products (e.g. hydrocarbons such as ethaneand propane and oxygenated hydrocarbons such as methanol, ethanol,propanol and butanol). Those who practice such processes continue toseek improved processes and catalysts which provide a product mixturethat favors selectivity to oxygenates over hydrocarbons, with at leastsome practioners preferring certain oxygenates, such as propanol, overother oxygenates, such as methanol. Such a preference stems, at least inpart, from ease of converting C₂ to C₆ oxygenates to correspondingolefins relative to challenges in converting methanol to an olefin.

Anderson-type heteropoly compounds may be represented by general formula[A]^(n+)[XM₆O₂₄H_(x)]^(n−) (with X being a heteroatom such as Al, ortransition metal such as Co, Ni, Rh, located at the center. A is cationsuch as H⁺, (NH₄ ⁺), alkali metal ion, metal ion selected fromtransition metal ions, M being at least one of Mo and W), and n⁻ is netnegative charge of anion part and n+ is net positive charge of thecation. Anderson-type heteropoly compounds are classified into theA-type (x=0) and the B-type (x=6) by the number of attached protons,although some polyanions with x other than 0 or 6 have also beenreported.

K. Nomiya et al., in “Anderson-Type Heteropolyanions of Molybdenum (VI)and Tungsten (VI)”, Polyhedron, Volume 6, Number 2, pages 213-218(1987), disclose, in part, an investigation of B-type molybdopolyanions,especially those that contain a divalent metal ion (Zn(II), Cu(II),Co(II) or Mn(II)) other than Ni(II). They also investigate mixed Ni(II)polyanions where M in the above formula is a mixture of molybdenum (Mo)and tungsten (W).

C. Cabello et al., in “Anderson type heteropolyoxomolybdates incatalysis: 1. (NH₄)₃[CoMo₆O₂₄H₆].7H₂O/γ-Al₂O₃ as alternative ofCo—Mo/γ-Al₂O₃ hydrotreating catalysts”, Applied Catalysis A: General197, pages 79-86 (2000), present teachings about a method of preparingCo—Mo/γ-Al₂O₃ HDS (hydrodesulfurization) catalysts using the(NH₄)₃[CoMo₆O₂₄H₆].7H₂O Anderson type heteropolyoxomolybdate supportedon γ.Al₂O₃.

C. I. Cabello et al., in “Catalysts based on RhMo₆ heteropolymetallates.Bulk and supported preparation and characterization”. Studies in SurfaceScience and Catalysis, 143, Elsevier Science B. V. (2002), pages565-572, refer to prior research on a series of hexametallates namedAnderson [XM₆O₂₄H₆]³⁻ where M=Mo, W or Mo_((6-x))W_(x) and X═Co(III),Rh(III), Fe(III), Mi(II), Cu(II), Fe(VI), etc. that enables design andpreparation of a variety of mixed by- or tri-metallic phases that showstructural and redox properties and potential use in heterogeneouscatalysis applications like hydrotreating and ammoxidation.

I. L. Botto et al., in “(NH₄)₆[TeMo₆O₂₄].7H₂O Anderson phase asprecursor of the TeMo₅O₁₆ catalytic phase: thermal and spectroscopicStudies”, Materials Chemistry and Physics 47 (1997) pages 37-45,characterize Anderson-type heteropolyanion of formula [XMo₆O₂₄H₆]^(n−)where X is, for example, Te, Fe, Co, Al, Ga, Rh, Ni, or Zn.

T. Liu et al., in “Structures and Catalytic Activity of Pt—Mo BimetallicEnsembles Derived from a New Planar [PtMo₆O₂₄]⁸⁻ HeteropolyanionSupported on Al₂O₃ and SiO₂ ”, Journal of Catalysis 135 (1992), pages367-385, present teachings about the title materials in ethenehydrogenation and ethane hydrogenolysis.

C. Lamonier et al., in “Molybdocobaltate cobalt salts: New startingmaterials for hydrotreating catalysts”, Applied Catalysis B:Environmental 70, pages 548-556 (2007) deal with use of Andersonheteropolyanions as alternative starting materials to ammoniumheptamolybdate and cobalt nitrate for preparation of hydrotreatment(e.g. hydrodesulfurization of thiophene) oxidic precursors. They teachpreparation of ammonium salts of the Anderson molybdocobaltate((NH₄)₃[CoMo₆O₂₄H₆]) or molydoaluminate ((NH₄)₃[AlMo₆O₂₄H₆]).

British Patent (GB) 2 151 616 (Jackson) discloses a method for preparingoxygenated hydrocarbons (e.g. methanol, ethanol and propanol) bycontacting syngas at an elevated temperature with a catalyst comprisinga Group VIII (Periodic Table of the Elements) metal component (iron(Fe), cobalt (Co), nickel (Ni), Ru, Rh, palladium (Pd), osmium (Os),iridium (Ir), and platinum (Pt), especially rhodium (Rh)) supported ontungsten oxide or molybdenum oxide.

U.S. Pat. No. 4,749,724 (Quarderer et al.) discloses a Fischer-Tropschreaction to form alcohols from syngas using a catalyst containing atleast one element selected from Mo, W and Re in free or combined form,an alkali metal or alkaline earth metal promoter, and, optionally, asupport. The catalyst may contain limited quantities of components suchas zinc (Zn), copper (Cu) and Co.

In some aspects, this invention is a process for converting synthesisgas to an oxygenate, which process comprises contacting a mixture ofhydrogen and carbon monoxide with a transition metal-containing,Anderson-type heteropoly compound catalyst under conditions oftemperature, pressure and gas hourly space velocity sufficient toconvert said mixture to at least one alcohol wherein the alcoholcontains from one carbon atom to six carbon atoms, the catalyst having astructure represented by general formula (A)_(x)[M₁Mo_(y)W_(6-y)]M₂,wherein A is H⁺, an ammonium ion (NH₄)⁺, or an alkali metal ion, M₁ isat least one of aluminium, zinc or a transition metal selected fromiron, ruthenium, chromium, rhodium, copper, cobalt, nickel, palladiumand iridium, M₂ is an optional modifier metal that is at least one metalselected from an alkali metal, an alkaline earth metal and a transitionmetal selected from a group consisting of rhenium, chromium, palladium,cobalt, iridium, nickel, platinum, ruthenium and osmium, x is an integerwithin a range of from 3 to 4 and y is an integer within a range of from0 to 6.

The conditions of temperature, pressure and gas hourly space velocityinclude at least one of a temperature within a range of from 200 degreesCelsius (° C.) to 450° C., a pressure within a range of from 200 psig(1.38 MPa) to 4,000 psig (24.58 MPa) or a gas hourly space velocity iswithin a range of 300 hr⁻¹ to 25,000 hr⁻¹.

The mixture of hydrogen and carbon monoxide has a ratio of gaseoushydrogen (H₂) to carbon monoxide (CO) within a range of from 10:1 to1:10.

The above catalysts include an Anderson-type heteropoly compound portionand, optionally, a support portion. When the catalysts include a supportportion, the support is present in an amount within a range of fromgreater than 0 weight percent (wt %) to no more than 95 wt %, preferablyfrom greater than or equal to 40 wt % to no more than (less than orequal to) 90 wt %, in each case based upon total catalyst weight. Whenthe catalysts include a support, the Anderson-type heteropoly compoundportion, (A)_(x)[M₁Mo_(y)W_(6-y)]M₂ (sometimes represented herein simplyas “[M₁Mo_(y)W_(6-y)]M₂”), is present in a complementary amount of fromat least 5 wt % up to, but not including, 100 wt %, again based on totalcatalyst weight. The complementary amount is preferably from greaterthan or equal to 10 wt % to no more than (less than or equal to) 60 wt%, again based on total catalyst weight.

Within the heteropoly compound portion, A is present in an amount withina range of from 0.6 wt % to 40 wt %, preferably from 2 wt % to 25 wt %,M₁ is present in an amount within a range of from 1.4 wt % to 16 wt %,preferably from 4 wt % to 10 wt %, Mo is present in an amount within arange of from 0 wt % to 58 wt %, preferably from 12 wt % to 50 wt %, Wis present in an amount within a range of from 0 wt % to 73 wt %,preferably from 14 wt % to 45 wt %, and M₂, an optional component, ispresent in an amount within a range of from 0 wt % to 20 wt %,preferably from 2 wt % to 10 wt %, each wt % being based upon totalweight of the heteropoly compound.

M₁ is one or more metals selected from a group consisting of Rh, Co, Ni,Pd, Zn, Al, Ru, Fe, Pt, Mn, Cr, and Ir. M₁ is preferably Rh, Co or Ni.In some aspects, M₁ is a combination of cobalt and palladium, cobalt andrhodium, aluminum and rhodium, cobalt and aluminum, copper and cobalt,and zinc and cobalt, and y is 6.

The catalyst can also comprise more than one type of Andersonheteropolyoxo compounds. In some aspects, therefore, the catalystcomprises a mixture of at least two Anderson-type heteropoly compoundcatalysts, a first wherein M₁ is rhodium and a second wherein M₁ isselected from cobalt, iridium, copper, nickel, palladium, zinc,aluminum, iron, chromium, and ruthenium.

M₂, when present, is a modifier metal that is at least one metalselected from an alkali metal, an alkaline earth metal and a transitionmetal selected from a group consisting of rhenium (Re), Cr, Pd, Co, Ir,Ni, Pt, Ru, and Os. Alkali metals include sodium, potassium, lithium,rubidium, francium and cesium, with sodium, potassium and lithium beingpreferred. Alkaline earth metals include calcium, barium, strontium andradium with calcium or barium being preferred. Transition metal choicesfor M₂ are preferably Re, Cr, Pd, Co, Ir and Ni. M₂, when present, may,but is not required to, be the same metal as that chosen for M₁.

The support portion is preferably selected from silicas (SiO₂),zirconias (ZrO₂), aluminas (Al₂O₃), titanias (TiO₂), tungsten oxides(WO₃), magnesium oxides (MgO), zinc oxides (ZnO), a mixture of ZrO₂ andAl₂O₃, also known as zirconia-modified alumina, in either caserepresented as ZrO₂—Al₂O₃, magnesium aluminates (MgAl₂O₄), zincaluminates (ZnAl₂O₄), and MgO modified supports such as MgO—Al₂O₃ andMgO—SiO₂.

Anderson-type heteropoly compounds can be prepared according to themethods described by K, Nomiya et, al. (cited above). These methodsrelate to the preparation of A-type and B-type Anderson-type heteropolycompounds wherein M=Mo or W, and X is a divalent or trivalent metal ionsuch as Zn(II) or Al(III). The methods comprise in general preparingmolybdo- or tungsto-polyanions by adding an aqueous solution of mewlsulfates aluminas to a boiling aqueous solution of ammoniumheptamolybdate hydrate, further evaporating on a steam-bath, followed byfiltering the hot solution and cooling.

Arabic numerals designate Examples (Ex) of the present invention andcapital alphabetic letters indicate Comparative Examples (Comp Ex orCEx).

EX 1

Dropwise add, with stiffing and at room temperature (nominally 25° C.),0.5 grams (g) of a 30% aqueous solution of hydrogen peroxide (H₂O₂) toan aqueous solution of cobalt sulfate (CoSO₄.4H₂O, S. D. Fine, 1.04 gdissolved in 8 milliliters (mL) of water) to form a first solution. Addthe first solution, with stirring at 95° C. for 90 minutes, to a secondsolution of 7.65 g of ammonium heptamolybdate ((NH₄)₆Mo₇O₂₄.4H₂O, AcrosChemicals) dissolved in 65 mL water) form a third solution. Haltstiffing and allow the third solution to stand overnight. Recover fromthe third solution, by filtration and drying at a temperature of 80° C.,a green, crystalline powder represented as (NH₄)₃[CoMo₆O₂₄H₆].7H₂O, anAnderson-type heteropolyoxomolydate referred to herein by a shorthanddesignation as [CoMo₆].

EX 2

Replicate Ex 1, but substitute an aqueous solution of rhodium nitrate(Fluka, 0.45 g dissolved in 20 mL water) for the first solution andchange the second solution to 2.60 g of (NH₄)₆Mo₇O₂₄.4H₂O dissolved in40 mL water. Recover a yellow, crystalline powder from the thirdsolution. The powder is represented as (NH₄)₃[RhMo₆O₂₄H₆].7H₂O, anAnderson-type heteropolyoxomolydate referred to herein by a shorthanddesignation as [RhMo₆].

EX 3

Replicate Ex 1, but substitute an aqueous solution of aluminum nitrate(Al(NO₃)₃.9H₂O, Acros Chemicals, 1.16 g dissolved in 20 mL water) forthe first solution and change the second solution to 5.01 g of(NH₄)₆Mo₇O₂₄.4H₂O dissolved in 80 mL water. The powder is represented bya shorthand designation as [AlMo₆].

EX 4

Replicate Ex 1, but substitute an aqueous solution of copper sulfate(CuSO₄.5H₂O, S. D. Fine, 1.50 g dissolved in 40 mL water) for the firstsolution and change the second solution to 10.00 g of (NH₄)₆Mo₇O₂₄.4H₂Odissolved in 160 mL water. Recover a light blue, crystalline powder,represented as [CuMo₆], from the third solution.

EX 5

Replicate Ex 1, but substitute an aqueous solution of palladium chloride(PdCl₂, (Acros, 0.55 g dissolved in 20 mL water plus 4 drops ofconcentrated hydrochloric acid (HCl)) for the first solution and changethe second solution to 10.00 g of (NH₄)₆Mo₇O₂₄.4H₂O dissolved in 160 mLwater. Recover a yellow, crystalline powder, represented as [PdMo₆],from the third solution.

EX 6

Form a combined solution by mixing an aqueous solution of 2.80 g of[CoMo₆](from Ex 1) in 25 mL of water with 28.05 g of colloidal silica(34 wt % LUDOX colloidal suspension in deionized water, 158.7 millimoles(mmol) of colloidal silica) with vigorous stirring at room temperaturefor 90 minutes. Evaporate the combined solution to dryness at 100° C. toyield dried solids, then calcine the dried solids at 350° C. for 4 hrunder static air.

Mix, with stirring at room temperature, an aqueous solution of potassiumcarbonate (K₂CO₃ (CDH, 0.29 g dissolved in 20 mL of water)) with 11.01 gof the calcined solids, then evaporate the resulting mix to dryness at100° C. and calcine the dried mix at 350° C. in static air for 4 hr toyield a catalyst represented as [CoMo₆]/SiO₂/K.

Use a high pressure (1500 pounds per square inch gauge (psig) (10.34megapascals (MPa)) tubular microreactor system to evaluate catalystactivity for converting synthesis gas (syngas) to a mixed alcoholproduct. Place 1.5 g of the catalyst in the center of a stainless steelreactor (outer diameter (O.D.) of 0.25 inch (0.63 centimeter (cm))mounted vertically in a furnace. Use thermal mass controllers totransfer syngas (carbon monoxide to hydrogen (CO:H₂) ratio of 1:1) fromcompressed gas cylinders via an activated carbon purifier to thereactor, controlling reactor pressure via an air actuated back pressureregulator located downstream of the reactor. Use an electrically heatedaluminum block to control reactor temperature. Before introducing syngasto the reactor, pre-treat the catalyst in flowing hydrogen (H₂) (150standard cubic centimeters per minute (s-cm³/min)) at 330° C. for 4 hrs.After pretreatment, lower reactor temperature to 270° C., change the gasflow to 300 s-cm³/min of syngas and then pressurize the reactor to 1500psig (10.34 MPa).

Analyze products from the reactor by flowing gas phase reactor effluentat ambient pressure (nominally one atmosphere or 0.1 MPa) through a gassampling valve within a Siemens MAXUM™ gas chromatograph. To avoidcondensation of non-volatile products, heat all tubing downstream of thereactor to 160° C. Effect product separation by means of a REOPLEX™precolumn connected in series with a PORAPAK™ QS column. Quantifyeffluent from the PORAPAK column using a calibrated flame ionizationdetector (FID). Summarize results in Table 1 below.

EX 7

Replicate Ex 6, but first combine an aqueous solution of [PdMo₆](from Ex5) (1.41 g dissolved in 25 mL water)) and an aqueous solution of[CoMo₆](from Ex 1) (1.40 g in 25 mL water) at 90° C. and add thecombined solutions to 27.99 g of colloidal silica. Change the K₂CO₃solution to 0.21 g of K₂CO₃ dissolved in 20 mL of water and change theamount of calcined powder mixed therewith to 12 g. This Ex 7 produces acatalyst represented as [PdMo₆][CoMo₆]/SiO₂/K.

EX 8

Replicate Ex 7, but substitute an aqueous solution of ammonium rhodiummolybdate [RhMo₆](from Ex 2) (1.41 g dissolved in 25 mL water) for theammonium palladium molybdate solution. Change the amount of calcineddried solids to 11 g. This Ex 8 produces a catalyst represented as[RhMo₆][CoMo₆]/SiO₂/K.

EX 9

Replicate Ex 8, but substitute the aqueous solution of ammonium aluminummolybdate [AlMo₆] of Ex 3 for the aqueous solution of ammonium cobaltmolybdate and change the amount of [RhMo₆] dissolved in 25 mL of waterto 1.40 g. This Ex 9 produces a catalyst represented as[RhMo₆][AlMo₆]/SiO₂/K.

EX 10

Replicate Ex 7, but substitute an aqueous solution of [AlMo₆](1.41 gdissolved in mL water) for the aqueous solution of ammonium palladiummolybdate. This Ex 10 produces a catalyst represented as[CoMo₆][AlMo₆]/SiO₂/K.

EXAMPLE 11

Replicate Ex 7, but substitute an aqueous solution of [CuMo₆](from Ex4), 1.40 g dissolved in 25 mL water) for [PdMo₆] solution. This Ex 11produces a catalyst represented as [CuMo₆][CoMo₆]/SiO₂/K.

EX 12

Replicate Ex 11, but substitute an aqueous solution of ammonium zincmolybdate ((NH₄)₃[ZnMo₆O₂₄H₆](1.40 g dissolved in 25 mL water)) for the[CuMo₆] solution. Synthesize (NH₄)₃[ZnMo₆O₂₄H₆] by replicating Ex 4 andsubstitute zinc sulfate (ZnSO₄.7H₂O, S. D. Fine, 1.73 g) for coppersulfate (CuSO₄.5H₂O, S. D. Fine, 1.50 g) and the resultant compound ispresented as [ZnMo₆]. Change the amount of calcined powder mixed withthe K₂CO₃ solution to 11 g and the amount of K₂CO₃ in said solution to0.19 g. This Ex 12 produces a catalyst represented as[ZnMo₆][CoMo₆]/SiO₂/K.

TABLE 1 Ex 6 7 8 9 10 11 12 CO:H₂ 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Reaction339.8 340.2 339.8 340 339 340 340 temperature, ° C. Reaction 1502/ 1502/1526/ 1498/ 1502/ 1498/ 1500/ pressure, psig/MPa 10.36 10.36 10.52 10.3210.36 10.32 10.34 GHSV, h⁻¹ 7122 6024 5647 5127 6333 7067 6512 CO conv.,mol % 10.5 9.57 24.23 12.33 9.07 8.43 5 MeOH sel., mol % 20.07 23.6 21.424.6 19.4 22.5 23.6 EtOH sel, mol % 16.4 13.85 15.5 12.11 14.4 11.9 10.8PrOH sel, mol % 7.6 7.3 8.5 5.7 6.8 5.5 4.4 Alcohol sel, mol % 47 47.649 45 42.1 41.6 40 CH₄ sel, mol % 22 23.8 21.8 26.5 21.6 26.8 33 C₂ HCsel, mol % 14.4 14.5 13.9 15.1 16.7 17.4 15.7 HC sel, mol % 51.4 51.449.8 54.2 56.5 57.8 59.5 EtOH prod., g/kg_(cal)-h 68.5 46.26 130.4 52.8347.76 36.3 21.8 PrOH prod., g/kg_(cal)-h 23.7 18.3 53.45 18.35 15.8812.7 6.7 Alcohol/HC prod. ratio 1.56 1.62 1.68 1.47 1.3 1.28 1.21 MeOH =methanol; EtOH = ethanol; PrOH = propanol; CH₄ = methane; C₂ = twocarbon atoms; and HC = hydrocarbon; sel = selectivity; conv =conversion; prod = productivity

The data in Table 1 demonstrate that various Anderson heteropolycompound-based catalyst compounds effectively convert syngas to amixture of alcohols, with that of Ex 8 providing especially effectiveresults.

CEx A

Impregnate 1.8 g of a zirconia-alumina (ZrO₂—Al₂O₃) support at roomtemperature by dropwise adding thereto, with stirring at 50 rpm for 10min, an aqueous solution of rhodium nitrate (Rh(NO₃)₃, (Aldrich, 0.038 gdissolved in 2 mL water)). Dry the impregnated support at 120° C. for 5hrs, then calcine the dried, impregnated support at 400° C. for 4 hoursin static air to yield a catalyst represented as Rh/ZrO₂—Al₂O₃.

Use a high pressure tubular microreactor system to evaluate catalystperformance for converting a feedstream of carbon monoxide, and hydrogento alcohols. The system includes a stainless steel reactor tube having alength of 14 inches (35.6 centimeters (cm)) and an outside diameter of0.25 inch (0.64 cm) that is mounted vertically in an electrically heatedaluminum block that controls reactor temperature. Place 0.25 g of thecatalyst in the center of the reactor tube and place quartz beads at thetop and bottom of the tubes. Introduce feedstream gases (CO and H₂) tothe reactor along with nitrogen (N₂) as an internal standard fromcompressed gas cylinders, using a thermal mass controller to control gasflow rates for each of the feedstream gases and N₂. Use an activatedcarbon purifier to remove any metal carbonyls that may be present in theCO cylinder. Control reactor pressure using an air-actuated backpressure regulator located in a line connected to, but downstream of,the reactor.

Before introducing the feedstream and N₂ to the reactor, pretreat thecatalyst with flowing H₂ (1000 mL/hr) at 330° C. for 2 hrs. Afterpretreating the catalyst, lower reactor temperature to 280° C., changethe gas flowing through the reactor to a mixture of carbon monoxide (CO)and hydrogen (H₂) (1:1), and pressurize the reactor to 1000 psig (6.89megapascals (MPa)). Analyze products from the reactor by flowing reactoreffluent through a gas sampling valve within an Agilent gaschromatograph (GC) (model 7890A). Heat tubing between the reactor andthe GC to a temperature of 150° C. to 180° C. to minimize condensationof reaction products that are not volatile at lower temperatures. Effectproduct separation in the GC by flowing reactor effluent through threeparallel separation trains: a) a molecular sieve packed column and aHayeSep™ T packed column, (b) PoraBOND™ U capillary column, and (c) acapillary CP Wax separation column. Use the Siemens SIMATIC PCS7distributed automatic control systems for measurement, control, andsafeguarding of the reactor system and summarize analytical results inTable 2.

CEx B

Replicate CEx A, but change the amount of rhodium nitrate in thesolution to 0.046 g and substitute a magnesium aluminate (MgAl₂O₄)support for the ZrO₂—Al₂O₃ support to yield a catalyst represented asRh/MgAl₂O₄.

CEx C

Replicate CEx A, but change the amount of rhodium nitrate in thesolution to 0.046 g and add to the solution 0.165 g of ammoniumheptamolybdate ((NH₄)₆Mo₇O₂.2H₂O, Aldrich) to yield a catalystrepresented as RhMo₆ZrO₂—Al₂O₃.

CEx D

Replicate CEx C, but reduce the amount of ammonium heptamolybdate to0.068 g and add to the solution 0.098 g of ammonium metatungstate(H₂₆N₆O₄₀W₁₂, Aldrich,) to yield a catalyst represented asRhMo₃W₃/ZrO₂—Al₂O₃.

EX 13

Replicate CEx A, but change the support to 0.9 g of gamma-alumina(Aldrich), the aqueous solution to 0.1 g of the [RhMo₆] catalyst from Ex2 in 2 mL of water, the calcination pressure and catalyst performancepressure to that of Ex 1 and the pretreatment time to 3 hours to yield acatalyst represented as [RhMo₆]/Al₂O₃.

Evaluate catalyst performance using a high pressure parallel fixed bedreactor (PFBR) (PFBR System P/N; 132088 from Symyx™ Technologies Inc), amodular reactor composed of three bays, each of which contains 16reactor tubes. The tubes in each bay are enclosed in a stainless steelbell jar capable of being pressurized with nitrogen (N₂) at the samepressure as that used in each reaction. Load reactor tubes with 200microliters (L) of catalyst, reduce the catalyst in situ at 1500 psigfor three hours at 330° C. (heating rate of 5° C. per minute) using agaseous mixture of 90 volume % (vol %)) percent (vol %) hydrogen (H₂)and 10 vol % N₂, each vol % being based on total gaseous mixture volume.Cool the catalyst to 280° C.

Test the catalyst at a pressure of 1500 psig, temperatures as shown inTable 3 and GHSV of 6250 h⁻¹ using a feed mixture of carbon monoxide(CO) and hydrogen (H₂) (1:1 v/v %). Continue testing at 320° C. but at apressure of 90 bar (9 MPa), then return the pressure to 35 bar (3.5 MPa)and test at 340° C. Evaluate reactor tube effluent using a Siemensprocess GC. Replicate this catalyst test cycle two additional times andreport test results as an average of three test cycles in Table 3.

EX 14

Replicate Ex 13, but change the support to 0.9 g of SiO₂ (Aldrich) toyield a catalyst represented as [RhMo₆]/SiO₂.

EX 15

Replicate Ex 13, but change the support to 0.9 g of TiO₂ (Aldrich) toyield a catalyst represented as [RhMo₆]/TiO₂.

EX 16

Replicate Ex 13, but change the support to 0.9 g of ZrO₂ (Aldrich)) toyield a catalyst represented as [RhMo₆]/ZrO₂.

EX 17

Prepare a mixed zirconia-alumina precipitate by adding, at a rate of 5mL/minute, an aqueous solution of potassium carbonate (K₂CO₃ (CDH, 44.08g, 0.277 mol, dissolved in 250 mL of water)) to a stirred, 70° C.aqueous solution that contains both zirconium nitrate (ZrO(NO₃)₂ 2H₂O(Aldrich, 1.50 g, 6.49 mmol)) and aluminum nitrate (Al(NO₃)₃₉H₂O (S.D.Fine, 51.75 g, 0.09 mol) dissolved in 1000 mL of water.) After threehours, recover the precipitate by filtration and wash it repeatedly fourtimes with hot water (90° C.). Dry the washed precipitate at 120° C. for5 hours then calcine the dried precipitate at 450° C. in static air for4 hours to yield a compound referred as ZrO₂—Al₂O₃. Washing effectivelyremoves K₂CO₃, added as a precipitating agent, from the precipitate.

Replicate Ex 13, but change the substrate to the ZrO₂—Al₂O₃ compound toyield a compound represented as [RhMo₆]ZrO₂—Al₂O₃. Summarize results at1000 psig (6.89 MPa) in Table 2 and at 1500 psig (10.34 MPa) in Tables3, 4 and 5.

EX 18

Prepare a combined solution by adding an aqueous solution of magnesiumnitrate (Mg(NO₃)₂.6H₂O (S.D Fine, 1.03 g, 4 mmol, dissolved in 20 mL ofwater)) and aluminum nitrate (Al(NO₃)₃.9H₂O (Aldrich, 3.00 g, 8 mmol,dissolved in 30 mL of water)) to an aqueous solution containing urea(S.D. Fine, 4.80 g, 0.08 mol, dissolved in 20 mL of water). Transfer thecombined solution to a 100 mL Teflon coated autoclave, seal theautoclave and heat its contents at 180° C. for 20 hours. Cool theautoclave contents to ambient temperature, recover precipitate byfiltration, wash the precipitate three times with water. Dry the washedprecipitate in an air oven at 100° C. for 1 hour, then calcine the driedprecipitate at 700° C. for 4 hours in static air to yield a compoundreferred to as magnesium aluminate or MgAl₂O₄.

Replicate Ex 13, but change the substrate to MgAl₂O₄ to yield a compoundrepresented as [RhMo₆]/ZrO₂—Al₂O₃. Summarize results in Tables 3, 5 and6.

EX 19

Heat to boiling a combination of molybdenum oxide (MoO₃, SD Fine, 0.49g, 3.41 mmol) and sodium tungstate (Na₂WO₄.2H₂O, Chemport, 1.12 g, 3.41mmol) in 80 mL of water. Dropwise add an aqueous solution of rhodiumnitrate (Aldrich, 0.32 g, 1.03 mmol) dissolved in 20 mL of water to theabove solution to form a combined mixture, then allow the combinedmixture to stand overnight at 80° C. to allow solids to crystallize outof solution. Recrystallize the solids from water two times to yield acompound is represented as [RhW₃Mo₃].

At room temperature, impregnate 0.9 g of the same MgAl₂O₄ substrate asin Ex 18 with an aqueous solution of the [RhW₃Mo₃](0.1 g dissolved in 2mL water), then dry and calcine the impregnated substrate as in Ex 17,save for reducing calcining temperature to 350° C. to yield a compoundrepresented as [RhW₃Mo₃]/MgAl₂O₄. Evaluate catalyst performance as inCEx A and report in Table 2. Evaluate catalyst performance as in Ex 13and summarize results in Table 5.

EX 20

Use the apparatus of CEx A with a modification to allow the feedstreamto include ethylene and a modification of the procedure of CEx A toevaluate catalyst performance using the catalyst of Ex 19. Theprocedural changes are: a) increasing the amount of catalyst to 0.35 g;b) change the feedstream to a mixture of ethylene, CO, H₂ and N₂ in arespective volumetric ratio of 5:45:45:5; c) change the pressure towhich the reactor is pressurized to either 35 bar (3.5 megapascals (MPa)or 90 bar (9.0 MPa) as shown in Table 7 below; and d) use a temperatureas shown in Table 7. Summarize results in Table 7.

EX 21

Replicate Ex 19, but change the substrate to mixed zirconia-aluminateprepared as in Ex 17 above to yield a compound represented as[RhW₃Mo₃]/ZrO₂—Al₂O₃. Evaluate catalyst performance as in Ex 13 andsummarize results in Table 5.

EX 22

Add an aqueous solution containing cesium carbonate (Aldrich, 0.09mmol), sodium carbonate (Aldrich, 0.09 mmol) and lithium carbonate(Aldrich, 0.09 mmol) dissolved in 200 μL of water) to 200 milligrams(mg) of [RhMo₆]/MgAl₂O₄ prepared as in Ex 18 to form a modifiedcompound. Calcine the modified compound at 350° C. for four hours instatic air to yield a compound represented as [RhMo₆]—Cs—Na—Li/MgAl₂O₄.Evaluate catalyst performance as in Ex 17 at 1000 psig (6.89 MPa) andsummarize results in Table 2 and at 1500 psig (10.34 MPa) and summarizeresults in Table 6.

EX 23

Replicate Ex 22, but change the aqueous solution to potassium carbonate(Aldrich, 0.03 mmol dissolved in 200 μL of water) to yield a compoundrepresented as [RhMo₆]-K/MgAl₂O₄, evaluate only at 1500 psig (10.34 MPa)and summarize results in Table 6.

EX 24

Replicate Ex 23, but change the aqueous solution lithium carbonate(Aldrich, 0.09 mmol) dissolved in 200 μL of water) to yield a compoundrepresented as [RhMo₆]—Li/MgAl₂O₄ and summarize results in Table 6.

EX 25

At room temperature, add an aqueous solution of cobalt sulfate(CoSO₄.4H₂O (S.D. Fine, 1.04 g, 3.7 mmol, dissolved in 8 mL of water))to 30% H₂O₂(Ran Kem, 0.5 g) to form a first solution Add, with stirring,an aqueous solution of ammonium molybdate ((NH₄)₆Mo₇O₂₄.4H₂O) (SD Fine,7.65 g, 6.2 mmol, in 65 mL of water) to the first solution. Recover acrystalline material, [CoMo₆], as in Ex 19 above.

At room temperature, impregnate 0.9 g of ZrO₂— Al₂O₃ with an aqueoussolution containing 0.05 g of the [RhMo₆] from Ex 2 and 0.05 g of the[CoMo₆] prepared in this example, both dissolved in 1 mL of water. Dryand calcine the impregnated material as in Ex 19 to yield a compounddesignated as [RhMo₆][CoMo₆]/ZrO₂—Al₂O₃. Evaluate catalyst performanceat 1500 psig (10.34 MPa) and a gas hourly space velocity (GHSV) of 7000reciprocal hours (h⁻¹), and summarize analytical results in Table 4below.

EX 26

Replicate Ex 25, but substitute preparation of a chromium molybdenum[CrMo₆] crystalline material for preparation of the [CoMo₆] material.The first solution is an aqueous solution of chromium sulfate(Cr₂(SO₄)₃.4H₂O (CDH, 1.44 g, 3.1 mmol, dissolved in 20 mL of water).)Add the first solution, with stirring, to an aqueous solution of(NH₄)₆Mo₇O₂₄.4H₂O, SD Fine, 5.20 g, 4.2 mmol, in 80 mL of water).Recover a crystalline material [CrMo₆] as in Ex 19 above. Replicationyields a compound designated as [RhMo₆][CrMo₆]/ZrO₂—Al₂O₃. Summarizeanalytical results in Table 4 below.

EX 27

Replicate Ex 25, but substitute preparation of an iridium molybdenum[IrMo₆] material for preparation of the [CoMo₆] material. The firstsolution is an aqueous solution of iridium chloride (IrCl₃, S.D. Fine,0.6306 g, 1.888 mmol, dissolved in 10 mL of water). Add the firstsolution, with stirring, to an aqueous solution of (NH₄)₆Mo₇O₂₄.4H₂O, SDFine, 2 g, 1.62 mmol, in 40 mL of water). Recover a crystalline materialreferred to as [IrMo₆] using the procedure detailed in Ex 19 above.Replication yields a compound designated as [RhMo₆][IrMo₆]/ZrO₂—Al₂O₃.Summarize analytical results in Table 4 below.

EX 28

Replicate Ex 25, but substitute preparation of a nickel molybdenum[NiMo₆] material for preparation of the [CoMo₆] material. The firstsolution is an aqueous solution of nickel sulfate (NiSO₄.4H₂O (S.D.Fine, 1.14 g, 7.40 mmol, dissolved in 20 mL of water).) Add the firstsolution, with stirring, to an aqueous solution of (NH₄)₆Mo₇O₂₄.4H₂O (SDFine, 7.83 g, 6.34 mmol, in 100 mL of water). Recover a crystallinematerial referred to as [NiMo₆] using the procedure detailed in Ex 19above. Replication yields a compound designated as[RhMo₆][NiMo₆]/ZrO₂—Al₂O₃. Summarize analytical results in Table 4below.

EX 29

Replicate Ex 25, but substitute preparation of a palladium molybdenum[PdMo₆] material for preparation of the [CoMo₆] material. The firstsolution is an aqueous solution of palladium chloride (PdCl₂ (Aldrich,0.5497 g, 3.1 mmol, dissolved in 20 mL of water).) Add the firstsolution, with stirring, to an aqueous solution of (NH₄)₆Mo₇O₂₄.4H₂O (SDFine, 5.19 g, 4.2 mmol, in 80 mL of water). Recover a crystallinematerial referred to as [PdMo₆] using the procedure detailed in Ex 19above. Replication yields a compound designated as[RhMo₆][PdMo₆]/ZrO₂—Al₂O₃. Summarize analytical results in Table 4below.

EX 30

Combine, with stirring, an aqueous solution of rhenium chloride (ReCl₃(Aldrich, 0.08 g, dissolved in 6 mL of water)) and 1 g of ZrO₂—Al₂O₃.Evaporate solvent from the combination using a rotavap to leave a solidresidue. Dry and calcine as in Ex 17 to yield a support designated asRe/ZrO₂—Al₂O₃.

Dropwise add an aqueous solution of 0.05 g of the [RhMo₆] from Ex 2 in 6mL of water to the support, then dry and calcine the support as in Ex 19to yield a compound designated as [RhMo₆]Re/ZrO₂—Al₂O₃. Summarizeanalytical results in Table 4 below.

EX 31

At room temperature (25° C.), stir together an aqueous solution ofrhodium chloride (RhCl₃ (Aldrich, 0.20 g, 0.78 mmol, dissolved in 10 mLof water)) and an aqueous solution of ammonium meta-tungstate,((NH₄)₆W₂O₄₁.xH₂O, SD Fine, 1.1457 g, 0.3876 mmol, in 50 mL of water).Recover a crystalline material referred to as [RhW₆] using the proceduredetailed in Ex 19 above.

At room temperature, impregnate 0.9 g of the same MgAl₂O₄ substrate asin Ex 18 with an aqueous solution of the [RhW₆](0.1 g dissolved in 2 mLwater), dry the impregnated substrate at 120° C. for 5 hours, thencalcine the dried, impregnated substrate at 350° C. in static air for 4hours to yield a compound represented as [RhW₆]/MgAl₂O₄. Evaluatecatalyst performance as described above at 1500 psig (10.34 MPa) andsummarize results in Table 5 below.

EX 32

Replicate Ex 20, but use the catalyst from Ex 31. Summarize results inTable 7 below.

EX 33

Replicate Ex 31, but change the substrate to the mixedzirconia-aluminate prepared as in Ex 17 above to yield a compoundrepresented as [RhW₆]/ZrO₂—Al₂O₃. Summarize catalyst evaluation resultsin Table 5 below.

EX 34

Replicate Ex 25, but substitute MgAl₂O₄ for ZrO₂—Al₂O₃, and substitutepreparation of iron molybdenum [FeMo₆] crystalline material forpreparation of the [CoMo₆] material. The first solution is an aqueoussolution of ferric ammonium sulfate (NH₄Fe(SO₄)₂.12H₂O (Aldrich, 1.5 g,3.1 mmol, dissolved in 20 mL of water)). Add the first solution, withstirring, to an aqueous solution of (NH₄)₆Mo₇O₂₄.4H₂O (SD Fine, 5.20 g,4.2 mmol, in 80 mL of water). Recover a crystalline material referred toas [FeMo₆] using the procedure detailed in Ex 19 above. Replicationyields a compound designated as [RhMo₆][FeMo₆]/MgAl₂O₄. Summarizeanalytical results in Table 4 below.

EX 35

Replicate Ex 20, but use the catalyst from Ex 34. Summarize results inTable 7 below.

TABLE 2 CO S(p- Temp Conv S(Alc) ROH) S(HC) Catalyst Ex. No. ° C. % % %% Rh/ZrO₂—Al₂O₃ CEx A 300 0.48 18.89 2.30 81.11 Rh/ZrO₂—Al₂O₃ CEx A 3200.99 11.79 1.09 88.21 RhMo/ZrO₂—Al₂O₃ CEx C 300 1.31 46.79 8.02 53.21RhMo/ZrO₂—Al₂O₃ CEx C 320 2.41 31.89 6.41 68.11 RhMo/ZrO₂—Al₂O₃ CEx C340 6.83 14.18 2.74 85.82 [RhMo₆]/ Ex 17 300 4.23 55.90 8.87 44.10ZrO₂—Al₂O₃ [RhMo₆]/ Ex 17 320 8.65 36.66 6.66 63.34 ZrO₂—Al₂O₃ [RhMo₆]/Ex 17 340 12.99 17.69 2.97 82.31 ZrO₂—Al₂O₃ Rh/MgAl₂O₄ CEx. B 300 0.6022.91 1.82 77.09 Rh/MgAl₂O₄ CEx. B 320 1.07 19.28 1.59 80.72RhMo₃W₃/MgAl₂O₄ CEx D 300 1.39 73.40 7.39 26.60 RhMo₃W₃/MgAl₂O₄ CEx D320 2.63 67.33 7.42 32.67 RhMo₃W₃/MgAl₂O₄ CEx. D 340 6.31 50.67 7.1549.33 [RhW₃Mo₃]/ Ex 19 300 1.15 70.75 11.83 29.25 MgAl₂O₄ [RhW₃Mo₃]/ Ex19 320 2.10 62.81 13.77 37.19 MgAl₂O₄ [RhW₃Mo₃]/ Ex 19 340 5.60 53.3913.50 46.61 MgAl₂O₄ S(Alc) = selectivity to total alcohols, S(HC) =selectivity to total hydrocarbons, S(p-ROH) = selectivity to primaryalcohols (ethanol + propanol). Each selectivity is expressed as CO₂—free value.

The data in Table 2 compare the performance of [RhMo₆] Andersonheteropoly compound-based catalysts with Rh and Rh—Mo containingcatalysts that have Rh or Rh and Mo contents equal to those of the[RhMo₆] catalysts. With the ZrO₂—Al₂O₃ support, the [RhMo₆] basedcatalyst of Ex 17 provides greater CO conversion and selectivity to bothalcohols in general and primary alcohols in particular than the Rhcatalysts of CEx A or the RhMo catalysts of CEx C. With the MgAl₂O₄support, the [RhW₃Mo₃] based catalyst of Ex 19 performs much betterresults in terms of the measured parameters than the Rh catalyst of CExB and better results in terms of selectivity to primary alcohols thanthe RhMo₃W₃ catalyst of CEx D.

TABLE 3 CO S(p- Temp conv S(Alc) ROH) S(HC) p- Catalyst Ex. No ° C. % %% % ROH/HC [RhMo₆]/Al₂O₃ Ex 13 300 5.20 10.66 0.00 37.20 0.00[RhMo₆]/Al₂O₃ Ex 13 320 10.16 7.43 0.41 57.16 0.01 [RhMo₆]/Al₂O₃ Ex 13340 17.32 4.28 0.00 78.85 0.00 [RhMo₆]/MgAl₂O₄ Ex 18 300 3.05 81.4018.90 13.72 1.38 [RhMo₆]/MgAl₂O₄ Ex 18 320 6.16 73.66 20.16 20.81 0.97[RhMo₆]/MgAl₂O₄ Ex 18 340 10.60 59.57 18.30 34.13 0.54 [RhMo₆]/SiO₂ Ex14 300 7.22 22.67 6.27 73.79 0.08 [RhMo₆]/SiO₂ Ex 14 320 16.84 11.102.11 85.93 0.02 [RhMo₆]/SiO₂ Ex 14 340 35.23 3.97 0.51 93.87 0.01[RhMo₆]/ZrO₂—Al₂O₃ Ex 17 300 3.87 65.70 34.71 23.97 1.45[RhMo₆]/ZrO₂—Al₂O₃ Ex 17 320 9.53 58.90 33.59 33.59 1.00[RhMo₆]/ZrO₂—Al₂O₃ Ex 17 340 16.97 50.94 28.47 42.54 0.67 [RhMo₆]/TiO₂Ex 15 300 19.59 28.88 3.90 60.78 0.06 [RhMo₆]/TiO₂ Ex 15 320 32.37 12.231.31 75.85 0.02 [RhMo₆]/TiO₂ Ex 15 340 56.91 5.14 0.34 87.60 0.00[RhMo₆]/ZrO₂ Ex 16 300 5.19 28.94 15.75 50.18 0.31 [RhMo₆]/ZrO₂ Ex 16320 6.95 32.60 18.49 54.01 0.34 [RhMo₆]/ZrO₂ Ex 16 340 6.93 34.17 19.7256.19 0.35 S(Alc) = selectivity to total alcohols, S(HC) = selectivityto total hydrocarbons, S(p-ROH) = selectivity to primary alcohols(ethanol + propanol). Each selectivity is expressed as CO₂— free value.

The data in Table 3 show that selectivity to primary alcohols is muchbetter with modified supports such as MgAl₂O₄ and ZrO₂—Al₂O₃ (Ex 17 and18) than with conventional supports like Al₂O₃ (Ex 13), SiO₂ (Ex 14),ZrO₂ (Ex 16) and TiO₂ (Ex 15)

TABLE 4 Experiments with Mixed Anderson S(p-ROH/ Catalyst Ex Temp COconv S(Alc) S(p-ROH) S(HC) HC) [RhMo₆]/ZrO₂—Al₂O₃ 17 300 3.87 65.7034.71 23.97 1.45 [RhMo₆]/ZrO₂—Al₂O₃ 17 320 9.53 58.90 33.59 33.59 1.00[RhMo₆]/ZrO₂—Al₂O₃ 17 340 16.97 50.94 28.47 42.54 0.67[RhMo₆][CrMo₆]/ZrO₂—Al₂O₃ 26 320 1.74 38.68 18.87 38.68 0.49[RhMo₆][CrMo₆]/ZrO₂—Al₂O₃ 26 340 3.99 39.18 19.78 47.76 0.41[RhMo₆][PdMo₆]/ZrO₂—Al₂O₃ 29 320 2.31 43.14 15.03 35.29 0.43[RhMo₆][PdMo₆]/ZrO₂—Al₂O₃ 29 340 6.21 41.15 19.01 45.83 0.41[RhMo₆][CoMo₆]/ZrO₂—Al₂O₃ 25 300 1.80 75.26 39.18 22.68 1.73[RhMo₆][CoMo₆]/ZrO₂—Al₂O₃ 25 320 3.86 61.98 33.88 31.40 1.08[RhMo₆][CoMo₆]/ZrO₂—Al₂O₃ 25 340 8.62 55.03 27.43 39.06 0.70[RhMo₆][NiMo₆]/ZrO₂—Al₂O₃ 28 300 1.93 71.94 33.09 23.02 1.44[RhMo₆][NiMo₆]/ZrO₂—Al₂O₃ 28 320 4.02 62.72 30.47 32.97 0.92[RhMo₆][NiMo₆]/ZrO₂—Al₂O₃ 28 340 7.68 50.95 24.71 44.30 0.56[RhMo₆][IrMo₆]/ZrO₂—Al₂O₃ 27 320 1.77 41.44 22.52 41.44 0.54[RhMo₆][IrMo₆]/ZrO₂—Al₂O₃ 27 340 3.40 39.91 21.49 46.93 0.46[RhMo₆]Re/ZrO₂—Al₂O₃ 30 320 1.84 52.21 24.78 43.36 0.57[RhMo₆]Re/ZrO₂—Al₂O₃ 30 300 0.62 37.04 11.11 44.44 0.25[RhMo₆]Re/ZrO₂—Al₂O₃ 30 340 4.10 49.44 25.84 45.69 0.57[RhMo₆][FeMo₆]/MgAl₂O₄ 34 300 1.63 83.84 14.14 6.57 2.15[RhMo₆][FeMo₆]/MgAl₂O₄ 34 320 3.25 75.00 15.14 10.92 1.39[RhMo₆][FeMo₆]/MgAl₂O₄ 34 340 4.63 59.13 14.14 23.91 0.59 S(Alc) =selectivity to total alcohols, S(HC) = selectivity to totalhydrocarbons, S(p-ROH) = selectivity to primary alcohols (ethanol +propanol). Each selectivity is expressed as CO₂— free value.

The data in Table 4 show that one may replace part of the [RhMo₆] with anon-Rh Anderson type precursor such as [CrMo₆](Ex 26), [NiMo₆](Ex 28),[CoMo₆](Ex 25), [PdMo₆](Ex 29) or [IrMo₆](Ex 27) or modify the [RhMo₆]with a metal such as Re (Ex 30), in each case reducing catalyst cost byeliminating some Rh, an increasingly expensive and decreasinglyavailable metal, with some tradeoff in catalyst performance. Ex 34suggests that mixed Anderson complexes supported on materials other thanAl₂O₃ also provide satisfactory results.

TABLE 5 Mo—W mixed Anderson Precursors S(p-ROH)/ Ex. CO S(HC) CatalystNo Temp conv S(Alc) S(p-ROH) S(HC) ratio [RhMo₆]/MgAl₂O₄ 18 320 5.7974.74 19.42 19.93 0.97 [RhMo₆]/MgAl₂O₄ 18 340 10.60 59.57 18.30 34.130.54 [RhMo₆]/ZrO₂—Al₂O₃ 17 320 9.53 58.90 33.59 33.59 1.00[RhMo₆]/ZrO₂—Al₂O₃ 17 340 16.97 50.94 28.47 42.54 0.67 [RhW₃Mo₃]/MgAl₂O₄19 320 8.96 71.70 33.68 19.30 1.75 [RhW₃Mo₃]/MgAl₂O₄ 19 340 21.81 60.0431.15 33.00 0.94 [RhMo₃W₃]/ZrO₂—Al₂O₃ 21 320 1.94 10.28 2.80 57.94 0.05[RhMo₃W₃]/ZrO₂—Al₂O₃ 21 340 4.82 28.32 16.78 55.24 0.30 [RhW₆]/MgAl₂O₄31 320 0.90 44.90 20.41 22.45 0.91 [RhW₆]/MgAl₂O₄ 31 340 1.94 37.6822.71 34.30 0.66 [RhW₆]/ZrO₂—Al₂O₃ 33 340 3.09 16.58 8.54 69.35 0.12S(Alc) = selectivity to total alcohols, S(HC) = selectivity to totalhydrocarbons, S(p-ROH) = selectivity to primary alcohols (ethanol +propanol). Each selectivity is expressed as CO₂— free value.

The data in Table 5 show that, while all Ex provide satisfactoryresults, a combination of a mixed metal Anderson-type heteropolycompound compound-based catalyst compositions and a MgAl₂O₄ support (Ex19) provide unexpectedly superior results relative to the othercombinations shown in Table 5.

TABLE 6 Effect of Alkali addition S(p- S(p- ROH)/ Ex. Temp CO convS(Alc) ROH) S(HC) S(HC) Catalyst No ° C. % % % % ratio [RhMo₆]/MgAl₂O₄18 300 3.05 81.40 18.90 13.72 1.38 [RhMo₆]/MgAl₂O₄ 18 320 6.16 73.6620.16 20.81 0.97 [RhMo₆]/MgAl₂O₄ 18 340 10.60 59.57 18.30 34.13 0.54[RhMo₆]—K/MgAl₂O₄ 23 300 2.19 83.25 30.46 13.20 2.31 [RhMo₆]—K/MgAl₂O₄23 320 4.32 70.43 30.43 26.09 1.17 [RhMo₆]—K/MgAl₂O₄ 23 340 7.60 57.7726.50 36.93 0.72 [RhMo₆]—Li/MgAl₂O₄ 24 300 2.76 91.26 16.18 4.53 3.57[RhMo₆]—Li/MgAl₂O₄ 24 320 4.53 86.64 17.46 9.05 1.93 [RhMo₆]—Li/MgAl₂O₄24 340 7.72 70.63 20.26 24.67 0.82 [RhMo₆]—Cs—Na—Li/MgAl₂O₄ 22 300 1.7089.08 23.56 6.32 3.73 [RhMo₆]—Cs—Na—Li/MgAl₂O₄ 22 320 4.22 75.34 27.9520.55 1.36 [RhMo₆]—Cs—Na—Li/MgAl₂O₄ 22 340 7.66 61.29 25.98 33.28 0.78S(Alc) = selectivity to total alcohols, S(HC) = selectivity to totalhydrocarbons, S(p-ROH) = selectivity to primary alcohols (ethanol +propanol). Each selectivity is expressed as CO₂— free value.

The data in Table 6 show that an alkali metal modification (Ex 22-24)leads to an increase in selectivity to alcohol or an increase inselectivity to primary alcohols relative to the same catalyst absent analkali metal modification (Ex 18). Even without the alkali metalmodification, the data for Ex 18 are satisfactory.

TABLE 7 Effect of additional ethylene co-feed Ethyl- S S ene CO Pro-Pro- S S Ex Temp Press, conv conv panol panal Ethane CO₂ Catalyst No °C. (MPa) (%) (%) (%) (%) (%) (%) [RhMo₃W₃]/MgAl₂O₄ 20 260 3.5 79.48 5.2153.26 7.11 35.78 0.65 [RhMo₃W₃]/MgAl₂O₄ 20 280 3.5 81.88 5.49 47.4811.92 36.78 0.80 [RhMo₃W₃]/MgAl₂O₄ 20 300 3.5 97.89 6.84 44.95 1.8842.05 2.81 [RhMo₃W₃]/MgAl₂O₄ 20 300 9.0 94.61 8.49 59.73 2.14 29.32 2.39[RhMo₆][FeMo₆]/MgAl₂O₄ 35 260 3.5 56.06 2.51 46.00 2.32 49.53 0.44[RhMo₆][FeMo₆]/MgAl₂O₄ 35 280 3.5 69.57 2.87 40.87 2.26 54.31 0.44[RhMo₆][FeMo₆]/MgAl₂O₄ 35 300 3.5 84.35 4.31 35.24 2.07 58.96 0.69[RhMo₆][FeMo₆]/MgAl₂O₄ 35 300 9.0 88.03 4.88 42.26 1.43 51.85 1.22[RhW₆]/MgAl₂O₄ 32 260 3.5 51.67 2.75 11.73 45.56 41.54 0.22[RhW₆]/MgAl₂O₄ 32 280 3.5 70.21 3.56 17.06 35.35 45.98 0.25[RhW₆]/MgAl₂O₄ 32 300 3.5 90.37 4.31 24.06 20.99 52.08 0.44[RhW₆]/MgAl₂O₄ 32 300 9.0 94.49 6.13 32.37 20.48 43.52 0.61 S meansselectivity

The data in Table 7 show that Anderson-type heteropoly compound basedcatalysts are efficient for a feed that contains ethylene in addition tocarbon monoxide and hydrogen.

1. A process for converting synthesis gas to an oxygenate, which processcomprises contacting a mixture of hydrogen and carbon monoxide with atransition metal-containing, Anderson-type heteropoly compound catalystunder conditions of temperature, pressure and gas hourly space velocitysufficient to convert said mixture to at least one alcohol wherein thealcohol contains from one carbon atom to six carbon atoms, the catalysthaving a structure represented by general formula(A)_(x)[M₁Mo_(y)W_(6-y)]M₂, wherein A is H⁺, an ammonium ion, or analkali metal ion, M₁ is at least one of aluminum, zinc or a transitionmetal selected from iron, ruthenium, chromium, rhodium, copper, cobalt,nickel, palladium and iridium, M₂ is an optional modifier that is atleast one metal selected from an alkali metal, an alkaline earth metaland a transition metal selected from a group consisting of rhenium,chromium, palladium, nickel, iridium and cobalt, x is an integer withina range of from 3 to 4 and y is an integer within a range of from 0 to6.
 2. The process of claim 1, wherein the catalyst comprises a mixtureof at least two Anderson-type heteropoly compound catalysts, a firstwherein M₁ is rhodium and a second wherein M₁ is selected from cobalt,iridium, copper, nickel, palladium, zinc, aluminum, iron, chromium, andruthenium.
 3. The process of claim 1, wherein the catalyst furthercomprises at least one catalyst support selected from silicas, aluminas,titanias, tungsten oxides, zirconias, magnesias, zinc oxides or mixturesthereof, and modified supports selected from zirconia-modified silicasand aluminas, magnesium aluminates, zinc aluminates, and magnesiummodified silicas and aluminas.
 4. The process of claim 1, wherein theconditions of temperature, pressure and gas hourly space velocityinclude at least one of a temperature within a range of from 200° C. to450° C., a pressure within a range of from 200 psig (1.38 MPa) to 4,000psig (24.58 MPa) or a gas hourly space velocity is within a range of 300hr⁻¹ to 25,000 hr⁻¹.
 5. The process of claim 1, wherein the mixture ofhydrogen and carbon monoxide has a ratio of hydrogen to carbon monoxidewithin a range of from 10:1 to 1:10.
 6. The process of claim 1, whereinM₁ is a combination of cobalt and palladium, cobalt and rhodium,aluminum and rhodium, cobalt and aluminum, copper and cobalt, and zincand cobalt, and y is
 6. 7. The process of claim 1, wherein the mixtureof carbon monoxide and hydrogen further comprises an amount of anolefin.
 8. The process of claim 7, wherein the olefin is ethylene.